Evaluation of the Coulomb energy in relativistic self-consistent-field theory

 Computational schemes are presented with which to evaluate the electrostatic Coulomb energy in relativistic molecular electronic structure calculations using a basis of four-component Dirac spinor amplitudes. We demonstrate that algorithms may be constructed and implemented which differ only in minor details from those in common use in nonrelativistic quantum chemistry, and that the four-component formalism is neither as complicated nor as expensive as has been suggested recently in the literature. Spherically symmetrical atomic basis sets are presented which indicate that accurate representations of the Coulomb energy may be obtained using modest expansions of the electronic density in a scalar auxiliary basis set of spherical harmonic Gaussian-type functions. Received: 15 April 2002 / Accepted: 15 May 2002 / Published online: 29 July 2002     

J-matrix method of scattering in one dimension: The nonrelativistic theory

We formulate a theory of nonrelativistic scattering in one dimension based on the J-matrix method. The scattering potential is assumed to have a finite range such that it is well represented by its matrix elements in a finite subset of a basis that supports a tridiagonal matrix representation for the reference wave operator. Contrary to our expectation, the 1D formulation reveals a rich and highly nontrivial structure compared to the 3D formulation. Examples are given to demonstrate the utility and accuracy of the method. It is hoped that this formulation constitutes a viable alternative to the classical treatment of 1D scattering problem and that it will help unveil new and interesting applications.     

Scaling behaviour of the Hellmann potential with different strength parameters

We are reporting the scaling behaviour of the bound state energies associated with the Hellmann potential, with different strength parameters, using the Laguerre basis. We show the existence of a crossover phenomenon for the energy spectrum; the scaling laws for bound states as we approach the continuum are calculated. Close to the bound–resonance phase transition region, state energies and wavefunctions for the Hellmann potential, with different strength parameters, have been studied.     

Analytical treatment of the oscillating Yukawa potential

Using a suitable Laguerre basis set that ensures a tridiagonal matrix representation of the reference Hamiltonian, we were able to evaluate in closed form the matrix elements of the generalized Yukawa potential with a complex screening parameter. This enabled us to treat analytically both the cosine and sine-like Yukawa potentials on equal footing and compute their bound states spectrum as the eigenvalues of the associated analytical matrix representing their Hamiltonians. Finally we used a carefully designed complex scaling method to evaluate the resonance energies and compared our results satisfactorily with those obtained in the literature for the cosine-like Yukawa potential.     

Computation of bound states for 2D potentials using discrete basis

Using a suitable Laguerre basis set that ensures a tridiagonal matrix representation of the reference Hamiltonian, we were able to evaluate in closed form the matrix representation of the associated Hamiltonian for two exactly solvable 2D potentials. This enabled us to treat analytically the full Hamiltonian and compute the associated bound states spectrum as the eigenvalues of the associated analytical matrix representing their Hamiltonians. Finally we compared our results satisfactorily with those obtained using the Gauss quadrature numerical integration approach.

PACS numbers: 03.65.Ge, 34.20.Cf, 03.65.Nk, 34.20.Gj     

New types of phase behaviour in binary mixtures of hard rod-like particles

The phase behaviour of binary mixtures of hard rod-like particles has been studied using Parsons—Lee theory (Parsons, J. D., 1979, Phys. Rev. A, 19, 1225); Lee, S. D., 1987, J. Chem. Phys., 87, 4972). The stability of the isotropic-nematic (I-N) transition with respect to isotropic—isotropic (I-I), and nematic—nematic (N-N) demixing is investigated. The individual components in the mixtures are modelled as hard cylinders of diameters D_i and lengths L_i (i = 1,2). The aspect ratios k_i = L_i/D_i of the components are kept fixed (with values of k ₁ = 15 and k ₂ = 150), and the phase behaviour of the mixtures is studied for varying diameter ratios d = D ₁/D ₂. When the diameter ratio is relatively large, e.g., for values of d = 50, component 1 may be considered a large colloidal particle, while the second component plays the role of a weakly interacting solvent. This mixture exhibits only an I-N phase transition which is driven by the excluded volume interaction between the large particles (no I-I or N-N demixing is seen). A decrease in the diameter ratio enhances the contribution of the smaller component to the free energy (especially in terms of the unlike excluded volume term), and I-I as well as N-N demixing transitions are observed. The character of the N-N transition is rather unusual, a single region bounded by a lower critical point (in the pressure—composition plane) is seen for a diameter ratio of d = 3.2, while two demixed nematic regions bounded by lower and upper critical points are observed for d = 3.13. A further decrease in the diameter ratio (e.g., to d = 3) leads to systems with a phase behaviour in which the two demixed N-N regions meet, giving rise to a large demixed region with very strong fractionation in composition, and no N-N critical points. The I-I demixing transition is always accompanied by a lower critical point and occurs for systems with intermediate size (diameter) ratios. A diameter ratio of d = 4.5 corresponds to systems with significant like and unlike excluded volume interactions, and in this case the I-N transition takes place over the whole composition range with weak fractionation and one azeotropic point. Surprisingly, the coexisting nematic phase is of lower packing fraction than the isotropic phase for some of the compositions, i.e., an inversion of packing fraction takes place. In addition to this, the longer rods can be less ordered that the shorter rods for certain values of the composition.     

Study of the 2-channel systems using the J-matrix method

ABSTRACT

The partial widths and the branching ratios have been calculated for 2-channel systems, using the diagonalisation of a 2-channel full Hamiltonian and the J-matrix quantities related to the free Hamiltonian, for resonance states with different orbital angular momentum ? (? = 0, 1, 2, 3) and different charge z (z = +1,?0,?? 1) for Noro and Taylor potential. Moreover, the 1- and 2-channel Morse potential have been investigated for the two diatomic molecules H₂ and LiH. The basis used is the Laguerre basis. Two approximate methods have been used to calculate the widths and the ratios associated with a spinless projectile?target system. Many results are reported here for the first time, including the results of ? ≠ 0 and z ≠ 0 in 2-channel Noro and Taylor potential, and the results for the two diatomic molecules. The comparison of our outcome with earlier studies, wherever possible, on energies, branching ratios and partial widths, is discussed.